CN112175010A - Synthesis method of hexafluorocyclotriphosphazene - Google Patents
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- CN112175010A CN112175010A CN202011114599.3A CN202011114599A CN112175010A CN 112175010 A CN112175010 A CN 112175010A CN 202011114599 A CN202011114599 A CN 202011114599A CN 112175010 A CN112175010 A CN 112175010A
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- hexafluorocyclotriphosphazene
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- 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 title claims abstract description 30
- 238000001308 synthesis method Methods 0.000 title abstract description 12
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000012025 fluorinating agent Substances 0.000 claims abstract description 16
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 239000002608 ionic liquid Substances 0.000 claims description 18
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical group [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 18
- 230000002194 synthesizing effect Effects 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 235000003270 potassium fluoride Nutrition 0.000 claims description 9
- 239000011698 potassium fluoride Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- BXOAIZOIDUQOFA-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;hydroxide Chemical compound [OH-].CCCC[N+]=1C=CN(C)C=1 BXOAIZOIDUQOFA-UHFFFAOYSA-M 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 27
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000000706 filtrate Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000010587 phase diagram Methods 0.000 description 4
- 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 3
- 239000011830 basic ionic liquid Substances 0.000 description 3
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 3
- UNEATYXSUBPPKP-UHFFFAOYSA-N 1,3-Diisopropylbenzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1 UNEATYXSUBPPKP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 241000208125 Nicotiana Species 0.000 description 2
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 2
- 229940073769 methyl oleate Drugs 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- -1 phosphazene compound Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
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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
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a synthesis method of hexafluorocyclotriphosphazene, which comprises the following steps: dissolving hexachlorocyclotriphosphazene in an organic solvent, adding a fluorinating agent and a catalyst, carrying out fluorination reaction, and then rectifying to obtain the target product, namely the hexachlorocyclotriphosphazene. The synthesis method of the hexafluorocyclotriphosphazene has the advantages of mild reaction temperature, simple process, easy operation, high yield, short time consumption, high purity, greenness, economy and convenience for industrial production.
Description
Technical Field
The invention belongs to the field of hexafluorocyclotriphosphazene, and particularly relates to a synthesis method of hexafluorocyclotriphosphazene.
Background
The phosphazene compound is an inorganic-organic hybrid compound formed by alternately arranging P-N. The phosphazene flame retardant has a good synergistic effect between phosphorus and nitrogen, has a high thermal decomposition temperature and a flame retardant effect, is low in smoke and toxic gas, and is an environment-friendly flame retardant material. Hexachlorocyclotriphosphazene is most representative in phosphazene compounds, and chlorine atoms in the hexachlorocyclotriphosphazene have high activity and are easily substituted by a plurality of nucleophiles, so that the hexachlorocyclotriphosphazene can be used for synthesizing phosphazene derivatives with various functional groups. The hexachlorocyclotriphosphazene is an important intermediate, and some derivatives of the hexachlorocyclotriphosphazene are high-end flame retardants and are widely applied to high-efficiency flame retardance of lithium batteries.
Patent CN109503664A discloses a synthesis method of hexafluorocyclotriphosphazene: in a non-polar solvent, under the action of a main catalyst glycol dimethyl ether homolog and a cocatalyst alcohol or phenol, hexachlorocyclotriphosphazene and a fluorinating agent undergo a fluorination reaction to prepare hexachlorocyclotriphosphazene. However, the synthesis method has the disadvantage that two catalysts are used, which increases the cost.
Patent CN105732718A discloses a synthesis method of hexafluorocyclotriphosphazene: in an organic solvent, under the action of a catalyst, polyethylene glycol or polyethylene glycol dimethyl ether, hexachlorocyclotriphosphazene and a fluorinating agent are used for preparing hexachlorocyclotriphosphazene. However, this method has a drawback that the reaction takes a long time.
Patent CN104788495A discloses a fluorination method of hexachlorocyclotriphosphazene and its derivatives: dissolving hexachlorocyclotriphosphazene in ionic liquid, namely taking the ionic liquid as a solvent, adding a fluorinating agent, and controlling the temperature at 130-280 ℃ to perform fluorination reaction for 10-16 h. The method has the following disadvantages: the reaction temperature is higher and the reaction time is long.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems in the prior art, the invention provides the method for synthesizing the hexafluorocyclotriphosphazene, which has the advantages of mild reaction conditions, simple and easily operated process, high yield, short time consumption, high purity, greenness, economy and convenience for industrial production.
The technical scheme is as follows: in order to achieve the above purpose, the synthesis method of hexafluorocyclotriphosphazene of the invention comprises the following steps: dissolving hexachlorocyclotriphosphazene in an organic solvent, adding a fluorinating agent and a catalyst, carrying out fluorination reaction, and then carrying out rectification (ice water bath condensation) to obtain the target product, namely the hexachlorocyclotriphosphazene.
Wherein the organic solvent is selected from any one or more of acetonitrile, 1, 4-dioxane, normal hexane, acetone, cyclohexane and tetrahydrofuran.
Preferably, the amount of the organic solvent added is 50% or less in terms of the solid content ratio (i.e., the mass of the solid hexachlorocyclotriphosphazene and the fluorinating agent is the total mass of the solid and the organic solvent).
Wherein the fluorinating agent is selected from potassium fluoride, sodium fluoride or lithium fluoride.
Wherein the molar ratio of the hexachlorocyclotriphosphazene to the fluorinating agent is 1: (6.1-6.5).
Wherein the catalyst is an ionic liquid catalyst selected from any one of [ Nbmm ] OH, [ Mmim ] DMP and [ Bmim ] OH.
Wherein: research on efficient removal of lignin from tobacco stems using [ Mmim ] DMP ionic liquids, anecdotal. basic ionic liquids, was prepared according to the relevant literature [ J ] university of hunan, vol 44, 12, 2017, where catalysts were used primarily for removal of lignin from tobacco stems.
Preparing [ Nbmm ] OH ionic liquid, WangJilin, Wanluol, Liuxiaojing and the like according to related documents, catalyzing and synthesizing methyl oleate [ J ] by morpholine basic ionic liquid, a journal of fuel chemistry, 2013, 41 (1): 85-90, wherein the catalyst is mainly used for catalyzing and synthesizing methyl oleate.
Preparing [ Bmim ] OH ionic liquid according to related documents, having light, WangYanjun, Zhang 20625G, Huang Chongpin, basic ionic liquid [ BMIM ] OH catalyzes m-diisopropylbenzene oxidation reaction kinetics research [ J ] industrial catalysis, 12 nd volume 22 nd phase 12 of 2014, wherein the ionic liquid catalyzes and oxidizes m-diisopropylbenzene reaction kinetics.
Wherein the dosage of the catalyst is 0.01-0.05% of the mass of the hexachlorocyclotriphosphazene.
Wherein the temperature of the fluorination reaction is 20-50 ℃ and the time is 2-3 h. Preferably, the temperature of the reaction is 30 to 35 ℃.
The invention relates to a method for synthesizing hexafluorocyclotriphosphazene.
The structural formula of the hexachlorocyclotriphosphazene is as follows:
the hexafluorocyclotriphosphazene synthesized by the method for synthesizing the hexafluorocyclotriphosphazene is applied to the lithium ion battery.
According to the synthesis method for preparing the hexachlorocyclotriphosphazene, under the action of an organic solvent and a catalyst, a fluorinating agent and the hexachlorocyclotriphosphazene are subjected to fluorination reaction, six chlorine atoms on the hexachlorocyclotriphosphazene are replaced by fluorine, and the hexachlorocyclotriphosphazene can be obtained through rectification.
Specifically, the reaction process in the invention is as follows:
has the advantages that: compared with the prior art, the invention has the following advantages:
the invention provides a brand new synthesis method of hexafluorocyclotriphosphazene, and the whole synthesis process has the advantages of mild reaction temperature, simple process, easy operation, high yield, short reaction time, simple post-treatment, less by-products, high purity, greenness, economy and convenience for industrial production. The synthesis method of the hexafluorocyclotriphosphazene can be used for synthesizing the hexafluorocyclotriphosphazene with high yield and high efficiency and is applied to the lithium ion battery.
Drawings
FIG. 1 is a liquid phase diagram of the starting material hexachlorocyclotriphosphazene in example 1;
FIG. 2 is a liquid phase diagram of the product hexafluorocyclotriphosphazene of example 1;
FIG. 3 is a mass spectrum of the product hexafluorocyclotriphosphazene of example 1.
Detailed Description
The present invention will be described in detail with reference to specific examples.
The experimental methods described in the examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified. The raw materials used in the present invention are commercially available.
Example 1
104.3g of hexachlorocyclotriphosphazene, 113.3g of potassium fluoride, 0.011g of ionic liquid catalyst [ Nbmm ] OH and 217.6g of anhydrous acetonitrile are placed in a flask with an electric stirrer, a thermometer and a reflux condenser tube for reaction at 30 ℃, the reaction is closed after 2 hours, the reaction is filtered, and the filtrate is rectified to obtain the hexachlorocyclotriphosphazene with the yield of 98.7 percent.
Wherein, the liquid phase diagram of the hexachlorocyclotriphosphazene of the raw material is shown in figure 1, and the liquid phase diagram and the mass spectrogram of the product are shown in figures 2 and 3, which indicates that the hexachlorocyclotriphosphazene is synthesized.
Example 2
104.3g of hexachlorocyclotriphosphazene, 113.3g of potassium fluoride, 0.011g of ionic liquid catalyst [ Nbmm ] OH and 217.6g of anhydrous acetonitrile are placed in a flask with an electric stirrer, a thermometer and a reflux condenser tube for reaction at 50 ℃, the reaction is closed after 3h, the reaction is filtered, and the filtrate is rectified to obtain the hexachlorocyclotriphosphazene with the yield of 98.1 percent.
Example 3
104.3g of hexachlorocyclotriphosphazene, 113.3g of potassium fluoride, 0.011g of ionic liquid catalyst [ Nbmm ] OH, 217.6g of 1, 4-dioxane are placed in a flask with an electric stirrer, a thermometer and a reflux condenser tube for reaction at 30 ℃, the reaction is closed after 2 hours, the reaction is filtered, and the filtrate is rectified to obtain the hexachlorocyclotriphosphazene with the yield of 86%.
Example 4
104.3g of hexachlorocyclotriphosphazene, 113.3g of potassium fluoride, 0.014g of ionic liquid catalyst [ Nbmm ] OH and 217.6g of tetrahydrofuran are placed in a flask with an electric stirrer, a thermometer and a reflux condenser tube, the reaction is carried out at 50 ℃, the reaction is closed after 3 hours, the reaction is filtered, and the filtrate is rectified to obtain the hexachlorocyclotriphosphazene with the yield of 93.3 percent.
Example 5
104.3g of hexachlorocyclotriphosphazene, 113.3g of potassium fluoride, 0.011g of ionic liquid catalyst [ Nbmm ] OH and 217.6g of cyclohexane are placed in a flask with an electric stirrer, a thermometer and a reflux condenser tube for reaction at 30 ℃, the reaction is closed after 2 hours, the reaction is filtered, and the filtrate is rectified to obtain the hexachlorocyclotriphosphazene with the yield of 95.8 percent.
Example 6
104.3g of hexachlorocyclotriphosphazene, 113.3g of potassium fluoride, 0.013g of ionic liquid catalyst [ Nbmm ] OH and 217.6g of acetone are placed in a flask with an electric stirrer, a thermometer and a reflux condenser tube, the reaction is carried out at 30 ℃, the reaction is closed after 2 hours, the filtration is carried out, and the filtrate is rectified to obtain the hexachlorocyclotriphosphazene with the yield of 96.7%.
Example 7
Example 7 is the same as example 1 except that: the adding amount of the organic solvent is added according to the solid content of 50%, the fluorinating agent is sodium fluoride, and the molar ratio of hexachlorocyclotriphosphazene to the fluorinating agent is 1: 6.1. the ionic liquid catalyst is [ Mmim ] DMP, the dosage of the ionic liquid catalyst is 0.05 percent of the mass of hexachlorocyclotriphosphazene, the temperature of the fluorination reaction is 20 ℃, and the time is 3 hours.
Example 8
Example 8 the same synthetic method as example 1, except that: the adding amount of the organic solvent is added according to the solid content of 50%, the fluorinating agent is lithium fluoride, and the molar ratio of hexachlorocyclotriphosphazene to the fluorinating agent is 1: 6.3. the ionic liquid catalyst is [ Bmim ] OH, the dosage of the ionic liquid catalyst is 0.03 percent of the mass of hexachlorocyclotriphosphazene, the temperature of the fluorination reaction is 40 ℃, and the time is 2.5 hours.
Comparative example 1
104.3g of hexachlorocyclotriphosphazene, 113.3g of potassium fluoride and 217.6g of acetonitrile are placed in a flask with an electric stirrer, a thermometer and a reflux condenser for reaction at 30 ℃, the reaction is closed after 2h, the filtration is carried out, and the filtrate is rectified to obtain the hexachlorocyclotriphosphazene with the yield of 36.7 percent.
It can be seen from comparative example 1 that the synthesis of hexafluorocyclotriphosphazene by fluorination according to the present invention uses a catalyst with high efficiency and can yield a product with high yield.
Claims (10)
1. A method for synthesizing hexafluorocyclotriphosphazene is characterized by comprising the following steps: dissolving hexachlorocyclotriphosphazene in an organic solvent, adding a fluorinating agent and a catalyst, carrying out fluorination reaction, and then rectifying to obtain the target product, namely the hexachlorocyclotriphosphazene.
2. The method for synthesizing hexafluorocyclotriphosphazene according to claim 1, wherein the organic solvent is selected from any one or more of acetonitrile, 1, 4-dioxane, n-hexane, acetone, cyclohexane and tetrahydrofuran.
3. The method for synthesizing hexafluorocyclotriphosphazene according to claim 1, wherein the amount of the organic solvent added is 50% or less in terms of solid content.
4. The method of synthesizing hexafluorocyclotriphosphazene according to claim 1, wherein the fluorinating agent is selected from potassium fluoride, sodium fluoride or lithium fluoride.
5. The method for synthesizing hexafluorocyclotriphosphazene according to claim 1, wherein the molar ratio of hexachlorocyclotriphosphazene to fluorinating agent is preferably 1: (6.1-6.5).
6. The method for synthesizing hexafluorocyclotriphosphazene as claimed in claim 1, wherein the catalyst is an ionic liquid catalyst selected from any one of [ Nbmm ] OH, [ Mmim ] DMP and [ Bmim ] OH.
7. The method for synthesizing hexafluorocyclotriphosphazene according to claim 1, wherein the amount of the catalyst is 0.01-0.05% by mass of the hexachlorocyclotriphosphazene.
8. The method for synthesizing hexafluorocyclotriphosphazene as claimed in claim 1, wherein the fluorination reaction is carried out at 20-50 ℃ for 2-3 h.
9. A hexafluorocyclotriphosphazene synthesized by the method of synthesizing a hexafluorocyclotriphosphazene of claim 1.
10. The use of the hexafluorocyclotriphosphazene synthesized by the method of claim 1 in a lithium ion battery.
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| CN101168493A (en) * | 2006-10-26 | 2008-04-30 | 中国石油化工股份有限公司 | Preparation method for fluorochlorobenzene |
| CN104788495A (en) * | 2015-04-14 | 2015-07-22 | 淄博蓝印化工有限公司 | Fluorination method for phosphonitrilic chloride trimer and derivatives thereof |
| CN107857780A (en) * | 2016-09-22 | 2018-03-30 | 微宏动力系统（湖州）有限公司 | A kind of synthetic method of fluoro phosphonitrile compound, fluoro phosphonitrile compound and battery electrolytic solution |
| CN109503664A (en) * | 2017-09-15 | 2019-03-22 | 张家港市国泰华荣化工新材料有限公司 | The preparation method of three phosphonitrile of hexafluoro ring |
| CN107759637A (en) * | 2017-11-16 | 2018-03-06 | 山东大学 | The fluoridation catalyst of a kind of phosphonitrile and phosphazene derivative and its synthetic method of fluoride |
| CN108314694A (en) * | 2018-02-02 | 2018-07-24 | 苏州贺康新材料科技有限公司 | A kind of preparation method of lithium battery electrolytes fire retardant |
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