CN102757026A - Preparation method of fluoro phosphonitrile compound - Google Patents
Preparation method of fluoro phosphonitrile compound Download PDFInfo
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- CN102757026A CN102757026A CN2012102492904A CN201210249290A CN102757026A CN 102757026 A CN102757026 A CN 102757026A CN 2012102492904 A CN2012102492904 A CN 2012102492904A CN 201210249290 A CN201210249290 A CN 201210249290A CN 102757026 A CN102757026 A CN 102757026A
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- phosphazene compound
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Abstract
The invention provides a preparation method of fluoro phosphonitrile compound. Under existence of polar solvent, the fluoro phosphonitrile compound and fluorinating agent are subjected to fluorinated reaction under the action of the potassium iodide to generate the fluoro phosphonitrile compound, and the fluoro phosphonitrile compound includes chain or ring compound. The fluoro phosphonitrile compound is fire retardant with excellent performance.
Description
Technical field
The present invention relates to the field of chemical synthesis, particularly relate to a kind of preparation method of fluoro phosphazene compound.At length say chloro phosphazene compound and fluorizating agent are carried out the fluorine substitution reaction under the effect of potassiumiodide, obtain the fluoro phosphazene compound.
Background technology
Phosphonitrile is as a kind of novel phosphorus-nitrogen containing flame retardant framework material, and its molecular formula is (PNX
2)
n(X is alkoxyl group, phenoxy or chlorine or fluorine element in the formula).Phosphazene derivative has outstanding flame retardant properties, is widely used in fields such as fire-retardant, biomedical material, elastomerics, electro-conductive material, and wherein fire retardant material is its topmost Application Areas.Through the kind and the quantity of regulation and control substituted radical, can obtain to satisfy all cpds of performance requriements.Existing at present multiple phosphonitrile compounds shows excellent flame-retardant and electrochemical stability in lithium cell.Therefore developing the phosphonitrile compounds has good application prospects and economic worth.
About fluoro phosphonitrile compounds relevant bibliographical information is arranged.J.Chem.Soc. report chloro phosphonitrile and Potassium monofluoride reacting by heating 22 days in sulfur dioxide liquid in, obtained the fluoro phosphazene compound.Reported chloro phosphazene compound and Sodium Fluoride synthesizing fluoro phosphazene compound under the condition that the oil of mirbane solvent of prepared fresh, less water exist among the Chem.and Indust..GB924565 has proposed the method for chloro phosphazene compound and Sodium Silicofluoride 98min reaction synthesizing fluoro phosphazene compound under hot conditions.J.Inorg.and Nucl.Chem. has reported the method for chloro phosphazene compound and tachyol synthesizing fluoro phosphazene compound.Chimica Acta. has proposed in the presence of solvent, is catalyzer with the crown ether, carries out the fluorine substitution reaction by chloro phosphazene compound and Potassium monofluoride and obtains the fluoro phosphazene compound.Having reported in Anorg.Chem. that chloro phosphazene compound and KSO2F react in the oil of mirbane solvent obtains the fluoro phosphazene compound.
The method of above synthesizing fluoro phosphazene compound; The special reagent of the long reaction time that has, the needs that need hot conditions, have that have, the expensive reagent of needs that has; These conditions are disadvantageous on producing, and except the production cost height, also have certain danger.
To the synthetic problem that exists that goes up of present fluoro phosphazene compound; The invention provides the method that the high yield of a kind of condition in gentleness obtains the fluoro phosphazene compound; This method is in the presence of potassiumiodide; Chloro phosphazene compound and fluorizating agent carry out the fluorine substitution reaction, obtain the fluoro phosphazene compound.This method reaction conditions is gentle, and yield is high, and production cost is low, is easy to realize suitability for industrialized production.
Summary of the invention
The object of the present invention is to provide a kind of compound method of fluoro phosphazene compound.
The chloro phosphazene compound of mentioning among the present invention has following structure: [NPCl
2]
nN=2～4 comprise that dimerization, trimerization and four polychlorostyrene are for phosphonitrile.
The fluoro phosphazene compound of mentioning among the present invention has following structure: [NPF
2]
nN=2～4 comprise that dimerization, trimerization and four polychlorostyrene are for phosphonitrile.
The method of synthesizing fluoro phosphazene compound of the present invention is in the presence of potassiumiodide, and chloro phosphazene compound and fluorizating agent are carried out the fluorine substitution reaction under the condition of gentleness, obtains the fluoro phosphazene compound.
The method of synthesizing fluoro phosphazene compound of the present invention, fluorizating agent are Sodium Fluoride, Potassium monofluoride, cesium fluoride, Calcium Fluoride (Fluorspan), plumbous fluoride etc., from complexity and the cost consideration that raw material obtains, and preferred fluorinated sodium or Potassium monofluoride, special preferred fluorinated sodium.
The method of synthesizing fluoro phosphazene compound of the present invention is under the condition that solvent exists, to carry out.Suitable solvent comprises acetonitrile, THF, dioxane isopolarity solvent.
The effect that the method for synthesizing fluoro phosphazene compound of the present invention, potassiumiodide can play accelerated reaction and improve transformation efficiency.
The method of synthesizing fluoro phosphazene compound of the present invention can adopt the method for fractionating method, according to the difference of reactant and product boiling point, reactant is separated with product; Also can, reaction adopt known distillation or crystalline method to separate and obtain product after finish.
The present invention adopts following technical scheme:
The method of synthesizing fluoro phosphazene compound of the present invention is in solvent, and under the effect of potassiumiodide, chloro phosphazene compound and fluorizating agent carry out the fluorine substitution reaction, obtain the fluoro phosphazene compound.
The method of synthesizing fluoro phosphazene compound of the present invention, fluorizating agent can be Sodium Fluoride, Potassium monofluoride, cesium fluoride, Calcium Fluoride (Fluorspan), plumbous fluoride etc., can use a kind of fluorizating agent separately, also can mix use by two or more fluorizating agent.
The method of synthesizing fluoro phosphazene compound of the present invention, the amount of fluorizating agent are 4～20 times of phosphonitrilic chloride compound amount.
The method of synthesizing fluoro phosphazene compound of the present invention, solvent is selected polar solvent, comprises acetonitrile, THF, dioxane etc.Can use a kind of solvent separately, also can two or more solvent use.The amount of solvent is 3～10 times of chloro phosphazene compound weight.
The method of synthesizing fluoro phosphazene compound of the present invention, the add-on of potassiumiodide are 0.01～10% of chloro phosphazene compound.
The method of synthesizing fluoro phosphazene compound of the present invention, temperature of reaction are 50～120 ℃, and temperature of reaction is not had special qualification.
The method of synthesizing fluoro phosphazene compound of the present invention can adopt the method for fractionating method, constantly product is distillated reaction system in reaction process, promotes to react completely.Also can, reaction adopt known distillation or crystalline method to separate and obtain product after finish.
Embodiment
Through specific embodiment the present invention is done further description below, but the present invention not only is defined in these instances.
Embodiment 1
Successively disposable with 175g (NPCl
2)
3, 300gKF, 3gKI add and be equipped with in the 2000ml flask of whisking appliance, TM, prolong, adds the 1000ml acetonitrile then, then at 80 ℃ with interior stirring reaction 5h.After reaction finishes, filter, adopt the distillatory method to collect product (NPF then
2)
3
Embodiment 2
In the 2000ml flask of whisking appliance, TM, separation column, prolong is housed, successively disposable adding 200g (NPCl
2)
3, 200gNaF, 1.5gKI, add the 1000ml dioxane then, then 80 ℃ with interior stirring reaction, in reaction process constantly with product (NPF
2)
3Distillate reaction system through separation column, reaction times 4h.Reaction can be adopted fractionated method purified product (NPF after finishing
2)
3
Embodiment 3
Successively disposable with 232g (NPCl
2)
4, 350gKF, 2gKI add and be equipped with in the 3000ml flask of whisking appliance, TM, prolong, adds the 1200ml THF then, then at 70 ℃ with interior stirring reaction 6h.After reaction finishes, filter, adopt the distillatory method to collect product (NPF then
2)
4
Embodiment 4
Successively disposable with 450g (NPCl
2)
4, 450gNaF, 10gKI add and be equipped with in the 5000ml flask of whisking appliance, TM, prolong, adds the 3000ml acetonitrile then, then refluxing and stirring reaction 6h.After reaction finishes, filter, adopt the distillatory method to collect product (NPF then
2)
4
Claims (6)
1. the preparation method of a fluoro phosphazene compound, it is characterized in that: in the presence of polar solvent, under the effect of potassiumiodide, chloro phosphazene compound and fluorizating agent carry out the fluorine substitution reaction, obtain the fluoro phosphazene compound.
2. the preparation method of fluoro phosphazene compound as claimed in claim 1 is characterized in that: described polar solvent is selected from a kind of in acetonitrile, THF or the dioxane, or is selected from wherein two or more and mixes and use.
3. like the preparation method of claim 1 and described fluoro phosphazene compound, it is characterized in that: the consumption of described polar solvent is 3～10 times of chloro phosphazene compound weight.
4. the preparation method of fluoro phosphazene compound as claimed in claim 1 is characterized in that: described fluorizating agent is selected from a kind of in Sodium Fluoride, Potassium monofluoride, cesium fluoride, Calcium Fluoride (Fluorspan) or the plumbous fluoride, or is selected from wherein two or more and mixes and use.
5. like the preparation method of claim 1 or 4 described fluoro phosphazene compounds, it is characterized in that: described fluorizating agent consumption is 4～20 times of phosphonitrilic chloride compound amount.
6. the preparation method of fluoro phosphazene compound as claimed in claim 1 is characterized in that: the add-on of described potassiumiodide is 0.01～10% of a chloro phosphazene compound.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210249290.4A CN102757026B (en) | 2012-07-18 | 2012-07-18 | A kind of preparation method of fluoro phosphonitrile compound |
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| CN201210249290.4A CN102757026B (en) | 2012-07-18 | 2012-07-18 | A kind of preparation method of fluoro phosphonitrile compound |
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| CN102757026A true CN102757026A (en) | 2012-10-31 |
| CN102757026B CN102757026B (en) | 2016-12-21 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214523A (en) * | 2013-04-01 | 2013-07-24 | 广州鸿森材料有限公司 | Preparation and use methods of high-temperature lithium-ion electrolyte additive and lithium ion battery containing additive |
| CN106083933A (en) * | 2016-06-13 | 2016-11-09 | 武汉海斯普林科技发展有限公司 | Hexafluoro ring three phosphonitrile and the preparation method of 1 ethyoxyl 1,3,3,5,5 5 fluorine ring three phosphonitrile |
| JP2018510130A (en) * | 2015-04-14 | 2018-04-12 | ▲ず▼博▲藍▼印化工有限公司 | Fluorination treatment method of phosphorus nitride chloride trimer and derivatives |
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2980495A (en) * | 1957-09-23 | 1961-04-18 | Olin Mathieson | Method of preparing polymeric phosphonitrilic fluoride |
| GB895969A (en) * | 1958-10-16 | 1962-05-09 | Albright & Wilson Mfg Ltd | Improvements relating to the production of cyclic phosphonitrilic fluorides |
| US3249396A (en) * | 1960-05-27 | 1966-05-03 | Albright & Wilson Mfg Ltd | Production of phosphonitrilic fluorides |
| CN1524313A (en) * | 2001-07-05 | 2004-08-25 | 株式会社普利司通 | Non-aqueous electrolyte cell, electrolyte stabilizing agent, and phosphazene derivative and method for preparation thereof |
-
2012
- 2012-07-18 CN CN201210249290.4A patent/CN102757026B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2980495A (en) * | 1957-09-23 | 1961-04-18 | Olin Mathieson | Method of preparing polymeric phosphonitrilic fluoride |
| GB895969A (en) * | 1958-10-16 | 1962-05-09 | Albright & Wilson Mfg Ltd | Improvements relating to the production of cyclic phosphonitrilic fluorides |
| US3249396A (en) * | 1960-05-27 | 1966-05-03 | Albright & Wilson Mfg Ltd | Production of phosphonitrilic fluorides |
| CN1524313A (en) * | 2001-07-05 | 2004-08-25 | 株式会社普利司通 | Non-aqueous electrolyte cell, electrolyte stabilizing agent, and phosphazene derivative and method for preparation thereof |
Non-Patent Citations (1)
| Title |
|---|
| 曾和平: "有机磷腈聚合物", 《化学通报》, no. 7, 31 December 1986 (1986-12-31), pages 7 - 10 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214523A (en) * | 2013-04-01 | 2013-07-24 | 广州鸿森材料有限公司 | Preparation and use methods of high-temperature lithium-ion electrolyte additive and lithium ion battery containing additive |
| CN103214523B (en) * | 2013-04-01 | 2016-01-06 | 广州鸿森材料有限公司 | A kind of method of preparation and use and the lithium ion battery comprising this additive of high temp. lithium ion electrolysis additive |
| JP2018510130A (en) * | 2015-04-14 | 2018-04-12 | ▲ず▼博▲藍▼印化工有限公司 | Fluorination treatment method of phosphorus nitride chloride trimer and derivatives |
| CN106083933A (en) * | 2016-06-13 | 2016-11-09 | 武汉海斯普林科技发展有限公司 | Hexafluoro ring three phosphonitrile and the preparation method of 1 ethyoxyl 1,3,3,5,5 5 fluorine ring three phosphonitrile |
| 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 |
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| Publication number | Publication date |
|---|---|
| CN102757026B (en) | 2016-12-21 |
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