- Preparation of the First Examples of Ansa-Spiro Substituted Fluorophosphazenes and Their Structural Studies: Analysis of C-H···F-P Weak Interactions in Substituted Fluorophosphazenes
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The reactions of fluorophosphazenes, endo ansa FcCH2P(S)(CH 2O)2[P(F)N]2(F2PN) (1) (Fc = ferrocenyl) and spiro [RCH2P(S)(CH2O) 2PN](F2PN)2 (R = Fc (2), C6H 5 (3)], with dilithiated diols have been explored. The study resulted in the formation of the first examples of ansa-spiro substituted fluorinated cyclophosphazenes as well as a bisansa substituted fluorophosphazene. The bisansa compound {1,3-[FcCH2P(S)(CH 2O)2]}{1,5-[CH2(CH2O) 2]}N3P3F2 (4) was found to be nongeminaly substituted with both the ansa rings in cis configuration, which is in stark contrast to the observations on cyclic chlorophosphazenes where geminal bisansa formation has been observed. The ansa-spiro compounds (5-7) underwent the ansa to spiro transformation leading to dispiro compounds in the presence of catalytic amounts of CsF at room temperature. Two of the ansa-spiro compounds, endo-{3,5-[FcCH2P(S)-(CH2O) 2]}{1,1-[CH2(CH2O)2]}N 3P3F2 (5) and endo-{3,5-[FcCH 2P(S)(CH2O)2]}{1,1-[FcCH 2P(S)(CH2O)2]}N3P3F 2 (6), were structurally characterized, and the crystal structures indicate boat-chair conformation as well as crown conformation for the eight-membered ansa rings. Weak C-H···F-P interactions observed in the crystal structures of the ansa-spiro substituted fluorophosphazene derivatives have been analyzed and compared with C-H···F-P interactions of other fluorinated phosphazenes and thionyl phosphazenes.
- Muralidharan,Elias, Anil J.
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- New results in the ammonolysis of hexafluoro-cyclo-triphosphazene: Crystal structure of P3N3F5-NH-P3 N3F4NH2
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The reaction of hexafluoro-cyclo-triphosphazene P3N3F6 with ammonia in acetonitrile has been studied. New compounds, (2-imino-2,4,4,6,6-pentafluoro-2λ5,4λ 5,6λ5-cyclo-triphosphaza-1,3,5-tri
- Richterová,Alberti,P?íhoda,Kubá?ek,Taraba,?ák
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- Synthesis method of hexafluorocyclotriphosphazene
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The invention discloses a synthesis method of hexafluorocyclotriphosphazene, which comprises the following steps: dissolving hexachlorocyclotriphosphazene in an organic solvent, adding a fluorinatingagent and a catalyst, carrying out fluorination reaction, and rectifying to obtain the target product hexafluorocyclotriphosphazene. The synthesis method of hexafluorocyclotriphosphazene has the advantages of mild reaction temperature, simple and easy-to-operate process, high yield, short time consumption, high purity, greenness, economy and convenience in industrial production.
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Paragraph 0032-0050
(2021/01/12)
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- Preparation method of hexafluorocyclotriphosphazene
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The invention discloses a preparation method of hexafluorocyclotriphosphazene, which comprises the steps of adding hexachlorocyclotriphosphazene and a fluorinating agent in a non-polar solvent in the presence of a catalyst, and carrying out a fluorination reaction to obtain the hexafluorocyclotriphosphazene, wherein the catalyst is a combined catalyst formed by ethylene glycol monomethyl ether and ethylene glycol monobutyl ether, the mass ratio of ethylene glycol monomethyl ether to ethylene glycol monobutyl ether is 1: (0.1-10), and the dosage of the combined catalyst is 0.1%-20% of the mass of hexachlorocyclotriphosphazene. The method has the advantages that the preparation time is short, the route is simple, the reaction is complete under the condition of proper proportion and dosage of the combined catalyst, and the boiling point of the combined catalyst is far higher than that of the product, so that the combined catalyst is easily separated from the product, and then the product is high in yield and high in purity.
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Paragraph 0019-0028
(2021/06/23)
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- Preparation method for hexafluorocyclotriphosphazene
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The invention discloses a preparation method for hexafluorocyclotriphosphazene. In a nonpolar solvent, under the effect of catalysts, hexachlorocyclotriphosphazene and a fluridizer generate fluorination reaction to produce hexafluorocyclotriphosphazene, and the nonpolar solvent is any one or a mixture of more of normal hexane, cyclohexane, toluene, chlorobenzene and xylene; the mass ratio of the nonpolar solvent to hexachlorocyclotriphosphazene is (2:1) to (4:1); the catalysts comprise a main catalyst and an auxiliary catalyst, wherein the main catalyst is a glycol dimethyl ether homologue, and the dosage of the main catalyst is 0.1 to 20 percent of the mass of hexachlorocyclotriphosphazene; the auxiliary catalyst is alcohols or phenols, and the dosage of the auxiliary catalyst is 0.1 to 20 percent of the mass of hexachlorocyclotriphosphazene; and the mass ratio of the dosages of hexachlorocyclotriphosphazene and the fluridizer is 1:1. The invention has the advantages that the reactiontemperature is not high, byproducts are less, reaction is thorough, the conversion rate is high, and after the reaction is completed, reaction liquid can directly react with other derivatives.
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Paragraph 0028-0033
(2019/04/04)
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- Preparation method of pentafluoro ethoxy cyclotriphosphazene
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The invention relates to the field of organic chemistry, in particular to a preparation method of pentafluoro ethoxy cyclotriphosphazene. The provided preparation method of pentafluoro ethoxy cyclotriphosphazene comprises the steps of 1, a fluorination reaction, wherein hexachloro cyclotriphosphazene reacts with hydrogen fluoride in the presence of a catalyst to prepare hexafluoro cyclotriphosphazene; 2, an etherification reaction, wherein the hexafluoro cyclotriphosphazene reacts with sodium alkoxide to prepare the pentafluoro ethoxy cyclotriphosphazene. The preparation method of the pentafluoro ethoxy cyclotriphosphazene has the advantages of being simple in reaction steps, reasonable in cost and suitable for large-scale industrialization.
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Paragraph 0049; 0059-0081
(2019/08/15)
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- Fluorophosphazene compound synthesis method, fluorophosphazene compound, and battery electrolyte
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The invention relates to a phosphazene synthesis method, and especially relates to a fluorophosphazene compound synthesis method. The fluorophosphazene compound synthesis method is characterized in that a chlorophosphazene compound and a fluorine salt undergo a one-step reaction in glycol ether to obtain the fluorophosphazene compound. The method has the characteristics of completeness in fluorination, single fluorination product, and simplicity in separation and purification.
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Paragraph 0024-0027; 0028-0037; 0038-0049; 0050-0053
(2018/04/21)
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- Preparation method of pentafluoroalkoxyl cyclotriphosphazene
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The invention discloses a preparation method of pentafluoroalkoxyl cyclotriphosphazene. The preparation method comprises the following steps: (1) adding hexachlorocyclotriphosphazene, a fluorinating agent and an organic solvent into a reaction container for reaction at a temperature between -30 DEG C and 80 DEG C to obtain a reaction solution containing hexafluorocyclotriphosphazene; (2) washing the reaction solution obtained in the step (1) with water, then carrying out standing for liquid separation to obtain an organic phase containing hexafluorocyclotriphosphazene, and distilling the organic phase to obtain the hexafluorocyclotriphosphazene; (3) adding an organic solvent, an alcohol, an acid binding agent and the hexafluorocyclotriphosphazene obtained in the step (2) into another reaction container to react at a temperature between -30 DEG C and 80 DEG C to obtain a reaction solution containing pentafluoroalkoxyl cyclotriphosphazene; (4) rectifying the reaction solution obtained inthe step (3) to obtain the pentafluoroalkoxyl cyclotriphosphazene. The method provided by the invention has the advantages of less side reactions and high yield of pentafluoroalkoxyl cyclotriphosphazene, has the high yield higher than 62%, and is suitable for industrial large-scale production.
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Paragraph 0016-0031
(2018/03/24)
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- Fluoridation catalyst of phosphonitrile and phosphonitrile derivative and synthetic method of fluoride
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The invention discloses a catalyst for fluoridation of phosphonitrile and a phosphonitrile derivative and a synthetic method of fluoride. The method comprises the following steps: dissolving chlorophosphonitrile or its derivative in an organic solvent, adding a fluorating agent and a catalyst and reacting for 1-48 h to obtain fluorophosphonitrile and a derivative thereof. The catalyst accounts for1-40% of total mass of the raw materials. The catalyst is an ionic liquid, has high melting/boiling point, is stable and green and environmentally-friendly, and has high catalytic efficiency. In addition, yield is greatly raised, and average yield reaches 98% and above.
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Paragraph 0035-0036; 0039-0040; 0043-0044; 0047-0048; 0051
(2018/03/24)
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- Preparation method of pentafluoro aromatic oxyl cyclotriphosphazene
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The invention discloses a preparation method of pentafluoro aromatic oxyl cyclotriphosphazene. The preparation method comprises: (1) adding hexachlorocyclotriphosphazene, a fluorinating agent and an organic solvent to a reaction container, and carrying out a reaction at a temperature of -30-80 DEG C to obtain a hexachlorocyclotriphosphazene-containing reaction liquid; (2) carrying out water washing on the reaction liquid obtained in the step (1), carrying out standing liquid layering to obtain a hexachlorocyclotriphosphazene-containing ogranic phase, and distilling the organic phase to obtainhexachlorocyclotriphosphazene; (3) adding an organic solvent, a phenol, an acid binder and the hexafluorocyclotriphosphazene obtained in the step (2) to another reaction container, and carrying out areaction at a temperature of -30-80 DEG C to obtain a reaction liquid containing pentafluoro aromatic oxyl cyclotriphosphazene; and (4) carrying out rectification on the reaction liquid obtained in the step (3) to obtain the pentafluoro aromatic oxyl cyclotriphosphazene. The preparation method of the present invention has advantages of less side reactions and high yield, and is suitable for industrial large-scale production, wherein the yield is not less than 60%.
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Paragraph 0016; 0027
(2018/03/25)
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- A Fluorination Method for Phosphonitrilic Chloride Trimer and Its Derivatives
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The present invention relates to a fluorination method for phosphonitrilic chloride trimer and its derivatives including using phosphonitrilic chloride or partially substituted phosphonitrilic chloride trimer as raw material to fluorinate with fluoridating agent in an ionic liquid to replace the chlorine in chloro-cyclotiphosphazene molecule. The present invention uses non-volatile and pollution free ionic liquids as solvent, and just controls a distillation temperature to get a hexafluorocyclotriphosphazene or derivatives thereof with high-purity. It overcomes the shortcoming of the average solvent system that the solvent forms azeotrope with products. The post-process is simple. The production rate is high, and the ionic liquid can be recycled. The present invention produces products with high purity.
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Paragraph 0017
(2018/05/17)
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- Cyclotriphosphazene compound, preparing method thereof, electrolyte for lithium secodary battery, and lithium secodary battery including the same
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A cyclotriphosphazene compound in which at least one fluorine is substituted with a group represented by formula 1 below, a preparing method thereof, an electrolyte for a lithium secondary battery including the cyclotriphosphazene compound, and a lithium secondary battery including the electrolyte are provided. Formula 1 is *A-B-CN, where A is a heteroatom having an unshared electron pair, * represents a combined site of the fluorinated cyclotriphosphazene compound with phosphor (P), and B is a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms.
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Paragraph 0135-0140
(2017/08/19)
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- A synthetic method of alkoxy(pentafluoro) or phenoxyl(pentafluoro) cyclotriphosphazene
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A synthetic method of alkoxy(pentafluoro) or phenoxyl(pentafluoro) cyclotriphosphazene is disclosed. The method includes (1) a step of subjecting hexachlorocyclotriphosphazene that is adopted as a raw material to a fluorination reaction in an organic solvent under a heating reflux state to obtain hexafluorocyclotriphosphazene by using an inorganic fluoride salt, and directly preparing the hexafluorocyclotriphosphazene through distillation and rectification; and (2) subjecting the hexafluorocyclotriphosphazene and an ethanol or a catalytic amount of a sodium alkoxide solution to a reaction under stirring at room temperature for 1-3 h, and performing vacuum distillation to obtain the alkoxy(pentafluoro) cyclotriphosphazene or phenoxyl(pentafluoro) cyclotriphosphazene. Product purity is 99% (GC). The method has characteristics of mild reaction conditions, low energy consumption, and simple process steps. A product of the step (1) can be directly used for the next reaction without the need of purification.
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Paragraph 0017; 0019; 0021; 0023
(2017/08/28)
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- ELECTROLYTE SOLUTION FOR NONAQUEOUS SECONDARY BATTERIES, AND SECONDARY BATTERY
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The present invention provides a nonaqueous electrolyte solution, which can improve flame retardancy and ameliorate performances of a battery without deteriorating the basic battery performance as far as possible, and a secondary battery. The nonaqueous electrolyte solution is a nonaqueous electrolyte solution for a secondary battery that contains metal salts including ions of metals belonging to group 1 or 2 of the periodic table and a specific cyclic compound having phosphorus and nitrogen atoms in a non-protonic solvent. The non-protonic solvent is a solvent that contains at least one kind of carboxylic acid ester compound and carbonic acid ester compound, and a ratio (M PN /Ms) between a mass (Ms) of the non-protonic solvent containing the metal salts and a mass (M PN ) of the cyclic compound is 0.01 to 1.
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Paragraph 0380-0382
(2017/04/03)
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- Gas-phase on-line generation and infrared spectroscopic investigations of polyphosphazenes, (NPX2)3 where X = F, Cl and Br
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Gas-phase infrared spectra of polyphosphazenes (phosphonitrilic halides trimer), (NPX2)3 where X = F, Cl and Br have been recorded. The molecules were generated for the first time by an on-line process using solid (NPCl2)3 as a precursor passed over heated sodium fluoride and potassium bromide at about 550 and 700 °C for (NPF 2)3 and (NPBr2)3 production, respectively. The products were characterized by the infrared spectra of their vapors. The low-resolution gas-phase Fourier transform infrared spectra reported for the first time show strong bands centered at 1295, 1215 and 1200 cm -1, assigned to ν7(E′), in plane PN stretching mode of (NPX2)3, where X = F, Cl and Br, respectively.
- Allaf, Abdul W.
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p. 1499 - 1503
(2007/10/03)
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- Fluoridolysis of Cyclophosphazenes and Lineary Phosphazenes
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The fluorination of nongeminal trans P3N3Cl4(NEt2)2 and nongeminal transP3N3Cl3(NEt2)3 with the fluorination agent Et3N*0.6HF (B) occurs under retention yielding P3N3Cl2F2(NEt2)2 and P3N3F4(NEt2)2 of P3N3F3(NEt2)3, respectively. P3N3Cl6 is nearly quantitatively converted into P3N3F6. Po ly(dichlorophosphazene) reacts to a poly(difluorophosphazene), (PNF2)n, distinguished by a moderate solubility in THF.
- Loewe, C.,Riesel, L.
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