A Fluorination Method for Phosphonitrilic Chloride Trimer and Its Derivatives

Abstract

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.

Claims

1. A fluorination method for phosphonitrilic chloride trimer and derivatives thereof, comprising the following steps: dissolving a phosphonitrilic chloride trimer or derivatives thereof into an ionic liquid, adding a fluorinating agent to obtain a solution, and maintaining the solution in a temperature for fluorination; and, distilling the solution after flourination at atmospheric pressure to get a hexafluorocyclotriphosphazene or derivatives thereof with high-purity; wherein a chemical formula of the phosphonitrilic chloride trimer and derivatives thereof is: ##STR00003## wherein each of S.sub.1-S.sub.6 comprises at least on chlorine, and each of S.sub.1-S.sub.6 is selected from the group consisting of alkyl, alkoxy, fluoroalkoxy, aryl, carboxyl, hydroxy, cyanogroup, nitro, ether oxygen group and halogen.

2. The fluorination method for phosphonitrilic chloride trimer and derivatives thereof according to claim 1, wherein a chemical formula of the ionic liquid is: ##STR00004## wherein the substitution in the chemical formula is mono, binary or triple substitution, wherein each of R1, R2, R3 and R4 is selected from the group consisting of alkyl, alkoxy, aryl, carboxyl, hydroxy, cyanogroup, nitro, ether oxygen group and halogen, wherein each of R1, R2 and R3 and R4 have 0-20 carbon atoms; wherein the anion X is one or more selected from the group consisting F.sup., PF.sub.6.sup., BF.sub.4.sup., TFSI.sup., FSI.sup., BOB.sup. and ClO.sub.4.sup..

3. The fluorination method for phosphonitrilic chloride trimer and derivatives thereof according to claim 2, wherein each of R1, R2 and R3 is selected from the group consisting of: methyl, ethyl, propyl, butyl, phenyl or benzyl.

4. (canceled)

5. The fluorination method for phosphonitrilic chloride trimer and derivatives thereof according to claim 1, wherein the fluorinating agent is one or more selected from the group consisting of ammonium fluoride, lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, calcium fluoride, magnesium fluoride, aluminum fluoride, chromium fluoride, iron fluoride, cobalt fluoride, antimony fluoride, nickel fluoride, copper fluoride, zinc fluoride, titanium fluoride and rare earth fluorides.

6. The fluorination method for phosphonitrilic chloride trimer and derivatives thereof according to claim 5, wherein the fluorinating agent is sodium fluoride and/or potassium fluoride.

7. The fluorination method for phosphonitrilic chloride trimer and derivatives thereof according to claim 1, wherein the temperature for fluorination is 10-300 C., the flourination is carried out for 2-98 hours and a temperature for distillation is 40-300 C.

8. The fluorination method for phosphonitrilic chloride trimer and derivatives thereof according to claim 1, wherein the temperature for fluorination is 0 C.-130 C., the fluorination is carried for a time duration of 12-15 hours and the temperature for distillation is 10 C. higher than the boiling point of the product.

Description

DETAILED DESCRIPTION OF THE INVENTION

Embodiment 1

[0017] Take 0.1 mole phosphonitrilic chloride trimer and add it into a flask with 100 ml 1-benzyl-3-methylpyridinium hexafluorophosphate ionic liquid and then add 1 mole sodium fluoride. Fluoridate 10 hours at 130 C. and then distill at 60 C. to get high-purity hexafluorocyclotriphosphazene.

Embodiment 2

[0018] Take 0.1 mole ethoxy pentachloride cyclotriphosphazene and add it into a flask with 100 ml 1-allyl-3-methylimidazolium tetrafluoroborate ionic liquid and then add 1 mole sodium fluoride. Fluoridate 12 hours at 130 C. and then distill at 160 C. to get high-purity pentafluoro ethoxy cyclotriphosphazene.

Embodiment 3

[0019] Take 0.1 mole pentachloride trifluoro ethoxy cyclotriphosphazene and add it into a flask with flux unit and containing 100 ml 1-phenyl-3-methylimidazolium tetrafluoroborate ionic liquid and then add 1 mole potassium fluoride and 0.5 mole sodium fluoride. Fluoridate 20 hours at 200 C. and then distill at 180 C. to get high-purity pentafluoro ethoxy cyclotriphosphazene.

Embodiment 4

[0020] Take 0.1 mole dichloro tetrabutoxy cyclotriphosphazene and add it into a flask with flux unit and containing 100 ml 1-methyl-3-methylimidazolium tetrafluoroborate ionic liquid and then add 0.5 mole potassium fluoride and 0.5 mole calcium fluoride. Fluoridate 16 hours at 280 C. and then distill at 220 C. to get high-purity difluoro tetrabutoxy cyclotriphosphazene.

Embodiment 5

[0021] Take 0.1 mole pentachloride phenoxy cyclotriphosphazene and add it into a flask with flux unit and containing 100 ml 1-ethylene-3-methylimidazolium tetrafluoroborate ionic liquid and then add 0.8 mole potassium fluoride. Fluoridate 16 hours at 50 C. and then distill at 240 C. to get high-purity pentafluoro phenoxy cyclotriphosphazene.

Embodiment 6

[0022] Take 0.1 mole pentachloride phenoxy cyclotriphosphazene and add it into a flask with 50 ml 1-phenoxy-3-methylimidazolium tetrafluoroborate and 50 ml 1-allyl-3-imethylimidazolium hexafluorophosphate ionic liquid and then add 0.8 mole potassium fluoride and 0.2 mole zinc fluoride. Fluoridate 16 hours at 50 C. and then distill at 240 C. to get high-purity pentafluoro phenoxy cyclotriphosphazene.

[0023] What is claimed is: